In this work, the effect of hexyl branch content on thermal behavior of a fractionated ethylene/1-octene copolymer with emphasis on high temperatures was investigated. The ethylene/1-octene copolymer was carefully fractionated to different fractions with homogenous hexyl branch (HB) content by preparative temperature rising elution fractionation (P-TREF) method. The P-TREF fractions were thermally analyzed via differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and evolved gas analysis (EGA). The P-TREF profile showed a short chain branch distribution (SCBD) of around 1.24. A linear relationship between P-TREF elution temperature (ET) and methylene sequence length (MSL) was presented. The DSC curves exhibited a monolithically increase in melting temperature (Tm) as well as crystallization temperature (Tc) by decreasing short chain branch (SCB) content. The calculated values of lamellae thickness suggested a linear function of SCB content and Tm. The TGA studies of P-TREF fractions depicted a two-stage thermal degradation behavior: pre-degradation and main degradation stages. Tmax for both pre-degradation and main degradation stages was increased for fractions with less hexyl branch content. As an interesting point the pre-degradation stage was found more intensified for more linear fractions. The concentration of main products was found to be affected by the content of hexyl branches using Py-GC-MS.
Papageorgiou DG, Bikiaris DN, Chrissafis K (2012) Effect of crystalline structure of polypropylene random copolymers on mechanical properties and thermal degradation kinetics. Thermochimica Acta 543: 288-294
Pourtaghi-Zahed H, Zohuri GH (2012) Synthesis and characterization of ethylene-propylene copolymer and polyethylene using α-diimine nickel catalysts. J Polym Res 19: 1-8
Mirabella FM, Crist B (2004) Melting behavior of polyethylene/α-olefin copolymers: Narrow composition distribution copolymers and fractions from Ziegler–Natta and single-site catalyst products. J Polym Sci Pol Phys 42: 3416-3427
Liu Z, Chen S, Zhang J (2011) Preparation and characterization of ethylene-butene copolymer (EBC)/mica composites. J Polym Res 18: 2403- 2413
Zhang X-b, Li Z-s, Lu Z-y, Sun C-C (2002) Roles of branch content and branch length in copolyethylene crystallization: Molecular dynamics simulations. Macromolecules 35: 106- 111
Mauler RS, Galland GB, Scipioni RB, Quijada R (1996) The effect of the ethylene pressure on its reaction with 1-hexene, 1-octene and 4-methyl- 1-pentene. Polym Bull 37: 469-474
Gomari S, Ghasemi I, Karrabi M, Azizi H (2011) Organoclay localization in polyamide 6/ethylene-butene copolymer grafted maleic anhydride blends: the effect of different types of organoclay. J Polym Res 19: 1-11
Pourtaghi-Zahed H, Zohuri GH, Ahmadjo S (2014) Unique microstructure analysis of ethylene-propylene copolymer synthesized using catalytic system based on α-diimine nickel complexes: a comparative study by 13C NMR technique. J Polym Res 21: 1-10
Bensason S, Stepanov E, Chum S, Hiltner A, Baer E (1997) Deformation of elastomeric ethylene-octene copolymers. Macromolecules 30: 2436-2444
Rabiej S, Goderis B, Janicki J, Mathot V, Koch M, Groeninckx G, Reynaers H, Gelan J, Włochowicz A (2004) Characterization of the dual crystal population in an isothermally crystallized homogeneous ethylene-1-octene copolymer. Polymer 45: 8761-8778
Babu RR, Singha NK, Naskar K (2010) Effects of mixing sequence on peroxide cured polypropylene (PP)/ethylene octene copolymer (EOC) thermoplastic vulcanizates (TPVs). Part. II. Viscoelastic characteristics. J Polym Res 18: 31-39
Sehanobish K, Patel R, Croft B, Chum S, Kao C (1994) Effect of chain microstructure on modulus of ethylene–α-olefin copolymers. J Appl polym Sci 51: 887-894
Bensason S, Minick J, Moet A, Chum S, Hiltner A, Baer E (1996) Classification of homogeneous ethylene-octene copolymers based on comonomer content. J Polym Sci Pol Phys 34: 1301-1315
Brady JM, Thomas EL (1988) Effect of short-chain branching on the morphology of LLDPE-oriented thin films. J Polym Sci Pol Phys 26: 2385-2398
Mileva D, Zia Q, Androsch R (2010) Tensile properties of random copolymers of propylene with ethylene and 1-butene: Effect of crystallinity and crystal habit. Polym Bull 65: 623-634
Galland GB, Mauler RS, de Menezes SC, Quijada R (1995) 13C-NMR study of ethylene/1-hexene and ethylene/1-octene copolymers obtained using homogeneous catalysts. Poly Bull 34: 599- 604
Koivumäki J (1996) Properties of ethylene/1- octene, 1-tetradecene and 1-octadecene copolymers obtained with Cp2ZrCl2/MAO catalyst: Effect of composition and comonomer chain length. Polym Bull 36: 7-12
Guo N, Li L, Marks TJ (2004) Bimetallic catalysis for styrene homopolymerization and ethylene-styrene copolymerization. Exceptional comonomer selectivity and insertion regiochemistry. J Am Chem Soc 126: 6542-6543
Mileva D, Androsch R, Radusch H-J (2009) Effect of structure on light transmission in isotactic polypropylene and random propylene- 1-butene copolymers. Polym Bull 62: 561-571
Vanden Eynde S, Mathot V, Höhne G, Schawe J, Reynaers H (2000) Thermal behaviour of homogeneous ethylene-1-octene copolymers and linear polyethylene at high pressures. Polymer 41: 3411-3423
Starck P, Rajanen K, Löfgren B (2002) Comparative studies of ethylene–α-olefin copolymers by thermal fractionations and temperature-dependent crystallinity measurements. Thermochim Acta 395: 169-181
Mileva D, Androsch R, Radusch H-J (2008) Effect of cooling rate on melt-crystallization of random propylene-ethylene and propylene-1- butene copolymers. Polym Bull 61: 643-654
Alamo RG, Mandelkern L (1994) The crystallization behavior of random copolymers of ethylene. Thermochim Acta 238: 155-201
Abbas-Abadi MS, Nekoomanesh N.M, Yeganeh H, Bozorgi B (2013) The effect of melt flow index, melt flow rate, and particle size on the thermal degradation of commercial high density polyethylene powder. J Therm Anal Calorim 114: 1333-1339
Kebritchi A, Nekoomanesh M, Mohammadi F, Khonakdar HA (2015) The interrelationships between microstructure and melting, crystallization and thermal degradation behaviors of fractionated ethylene/1-butene copolymer. Iran Polym J 24: 267-277
Kebritchi A, Nekoomansh M, Mohammadi F, Khonakdar HA (2015) The ablative behavior of high linear chains and its role in the thermal stability of polyethylene: A combined P-TREF− TGA study. Polym Int 64: 1316-1325
Kebritchi A, Nekoomansh M, Mohammadi F, Khonakdar HA (2014) The role of 1-hexene comonomer content in thermal behavior of medium density polyethylene (MDPE) synthesized using Phillips catalyst. Polyolefins J 1: 117-129
Kebritchi A, Nekoomanesh H. M, Mohammadi F, Khonakdar HA (2017) Effect of Microstructure of high density polyethylene on catalytic degradation: A comparison between nano clay and FCC. J Polym Environ 21: 1-10
Cheruthazhekatt S, Pijpers TF, Mathot VB, Pasch H (2013) Combination of TREF, high-temperature HPLC, FTIR and HPer DSC for the comprehensive analysis of complex polypropylene copolymers. Anal Bioanal Chem 405: 8995-9007
Assumption H, Vermeulen J, Jarrett WL, Mathias LJ, Van Reenen A (2006) High resolution solution and solid state NMR characterization of ethylene/1-butene and ethylene/1-hexene copolymers fractionated by preparative temperature rising elution fractionation. Polymer 47: 67-74
Müller A, Hernandez Z, Arnal M, Sánchez J (1997) Successive self-nucleation/annealing (SSA): A novel technique to study molecular segregation during crystallization. Polymer Bull 39: 465-472
Joe D, Golling FE, Friedemann K, Crespy D, Klapper M, Müllen K (2014) Anisotropic Supports in Metallocene-Catalyzed Polymerizations: Templates to Obtain Polyolefin Fibers. Macromol Mater Eng 299: 1155-1165
Dorresteijn R, Nietzel S, Joe D, Gerkmann Y, Fink G, Klapper M, Müllen K (2014) Metallocene supported on porous and nonporous polyurethane particles for ethylene polymerization. J Polym Sci Pol Chem 52: 450-459
De Rosa C, Auriemma F, Villani M, Ruiz de Ballesteros O, Di Girolamo R, Tarallo O, Malafronte A (2014) Mechanical Properties and Stress-Induced Phase Transformations of Metallocene Isotactic Poly (1-butene): The Influence of Stereodefects. Macromolecules: 47: 1053-1064
Zhang M, Wanke SE (2003) Quantitative determination of short-chain branching content and distribution in commercial polyethylenes by thermally fractionated differential scanning calorimetry. Polym Eng Sci 43: 1878-1888
Kakugo M, Miyatake T, Mizunuma K (1991) Chemical composition distribution of ethylene- 1-hexene copolymer prepared with titanium trichloride-diethylaluminum chloride catalyst. Macromolecules 24: 1469-1472
Adisson E, Ribeiro M, Deffieux A, Fontanille M (1992) Evaluation of the heterogeneity in linear low-density polyethylene comonomer unit distribution by differential scanning calorimetry characterization of thermally treated samples. Polymer 33: 4337-4342
Hosoda S (1988) Structural distribution of linear low-density polyethylenes. Polym J 20: 383-397
Mortazavi SMM, Arabi H, Zohuri G, Ahmadjo S, Nekoomanesh M, Ahmadi M (2010) Copolymerization of ethylene/α-olefins using bis (2-phenylindenyl) zirconium dichloride metallocene catalyst: Structural study of comonomer distribution. Polym Int 59: 1258- 1265
Hosoda S, Nozue Y, Kawashima Y, Suita K, Seno S, Nagamatsu T, Wagener KB, Inci B, Zuluaga F, Rojas G (2010) Effect of the sequence length distribution on the lamellar crystal thickness and thickness distribution of polyethylene: Perfectly equisequential ADMET polyethylene vs ethylene/α-olefin copolymer. Macromolecules 44: 313-319
Gauthier E, Laycock B, Cuoq F-M, Halley P, George K (2013) Correlation between chain microstructural changes and embrittlement of LLDPE-based films during photo-and thermo-oxidative degradation. Polym Degrad Stabil 98: 425-435
Wilfong DL,Knight G (1990) Crystallization mechanisms for LLDPE and its fractions. J Polym Sci Pol Phys 28: 861-870
Zhang M, Lynch D, Wanke S (2001) Effect of molecular structure distribution on melting and crystallization behavior of 1-butene/ethylene copolymers. Polymer 42: 3067-3075
Hosoda S, Kojima K, Furuta M (1986) Morphological study of melt-crystallized linear low-density polyethylene by transmission electron microscopy. Die Makromol Chem 187: 1501-1514
Kebritchi A, Nekoomanesh H. M, Mohammadi F, Khonakdar HA (2014) The role of 1-hexene comonomer content in thermal behavior of medium density polyethylene (MDPE) synthesized using Phillips catalyst. Polyolefins J 2: 117-129
Pielichowski K, Njuguna J (2005) Thermal degradation of polymeric materials. Rapra Technology, Show bury, UK
Katritzky AR, Kuanar M, Slavov S, Hall CD, Karelson M, Kahn I, Dobchev DA (2010) Quantitative correlation of physical and chemical properties with chemical structure: Utility for prediction. Chem Rev 110: 5714-5789
Lattimer RP (1995) Pyrolysis field ionization mass spectrometry of polyolefins. J Anal Appl Pyrolys 31: 203-225
Mastral F, Esperanza E, Berrueco C, Juste M, Ceamanos J (2003) Fluidized bed thermal degradation products of HDPE in an inert atmosphere and in air–nitrogen mixtures. J Anal Appl Pyrolys 70: 1-17.
Poutsma ML (1990) Free-radical thermolysis and hydrogenolysis of model hydrocarbons relevant to processing of coal. Energy Fuels 4: 113-131
Kossiakoff A, Rice FO (1943) Thermal decomposition of hydrocarbons, resonance stabilization and isomerization of free radicals1. J Am Chem Soc 65: 590-595
Kebritchi, A., Nekoomanesh, M., Mohammadi, F., Khonakdar, H., & Wagenknecht, U. (2019). Thermal behavior of ethylene/1-octene copolymer fractions at high temperatures: Effect of hexyl branch content. Polyolefins Journal, 6(2), 127-138. doi: 10.22063/poj.2019.2295.1123
MLA
Abbas Kebritchi; Mehdi Nekoomanesh; Fereidoun Mohammadi; Hossein Khonakdar; Udo Wagenknecht. "Thermal behavior of ethylene/1-octene copolymer fractions at high temperatures: Effect of hexyl branch content". Polyolefins Journal, 6, 2, 2019, 127-138. doi: 10.22063/poj.2019.2295.1123
HARVARD
Kebritchi, A., Nekoomanesh, M., Mohammadi, F., Khonakdar, H., Wagenknecht, U. (2019). 'Thermal behavior of ethylene/1-octene copolymer fractions at high temperatures: Effect of hexyl branch content', Polyolefins Journal, 6(2), pp. 127-138. doi: 10.22063/poj.2019.2295.1123
VANCOUVER
Kebritchi, A., Nekoomanesh, M., Mohammadi, F., Khonakdar, H., Wagenknecht, U. Thermal behavior of ethylene/1-octene copolymer fractions at high temperatures: Effect of hexyl branch content. Polyolefins Journal, 2019; 6(2): 127-138. doi: 10.22063/poj.2019.2295.1123